The Journal of Organic Chemistry
Article
(
m, 7H), 6.37 (d, J = 15.5 Hz, 1H), 3.41 (s, 3H). 13C NMR (100
MHz, CDCl ) δ = 166.1, 143.5, 141.6, 135.1, 129.5, 129.4, 128.6,
ASSOCIATED CONTENT
Supporting Information
Copies of H NMR and C NMR spectra of all new compounds.
■
3
*
S
1
27.7, 127.5, 127.2, 118.7, 77.3, 76.7, 37.5.
-(4-Methoxyphenyl)-N-methyl-N-phenylacetamide (3t).
22.0 mg, 87% yield. Isolated by flash column chromatography
1
13
2
2
(
ethyl acetate/petroleum ether = 1:5, R = 0.5). Oil. IR (neat): ν
f max
3
1
8
7
6
061, 3036, 2999, 2953, 2934, 2910, 2835, 1728, 1645, 1635, 1614,
AUTHOR INFORMATION
595, 1514, 1495, 1454, 1373, 1300, 1248, 1179, 1121, 1034, 916, 855,
■
−1 1
22, 789, 773, 700, 557, 409 cm . H NMR (400 MHz, CDCl ) δ =
3
.43−7.32 (m, 3H), 7.12 (d, J = 7.2 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H),
*
.77 (d, J = 8.5 Hz, 2H), 3.77 (s, 3H), 3.39 (s, 2H), 3.27 (s, 3H). 13
C
Notes
NMR (100 MHz, CDCl ) δ = 171.3, 158.2, 144.0, 130.0, 129.6, 127.8,
1
3
The authors declare no competing financial interest.
27.6, 127.4, 113.7, 55.2, 39.9, 37.5. HRMS calcd for C H NO
16 18 2
+
(M + H), 256.1332; found, 256.1332.
7
a
ACKNOWLEDGMENTS
N-Methyl-N-phenylbenzamide (3u). 168.9 mg, 80% yield.
■
Isolated by flash column chromatography (ethyl acetate/petroleum
ether = 1:5, R = 0.5). H NMR (400 MHz, CDCl ) δ = 7.31−7.27 (m,
Financial support by the National Science Foundation of China
(21072223, 21272267), State Key Laboratory of Heavy Oil
Processing (2012-1-06), the Fundamental Research Funds for
the Central Universities, and the Research Funds of Renmin
University of China (10XNL017).
1
f
3
2
3
1
H), 7.25−7.18 (m, 3H), 7.18−7.10 (m, 3H), 7.06−7.00 (m, 2H),
.49 (s, 3H). 13C NMR (100 MHz, CDCl ) δ = 170.6, 144.8, 135.8,
3
29.5, 129.0, 128.6, 127.6, 126.8, 126.4, 38.3.
4
2
8
-Acetyl-8-azabicyclo[3.2.1]octan-3-one (3v).
120.3 mg,
7
2% yield. Isolated by flash column chromatography (ethyl acetate/
REFERENCES
■
petroleum ether = 1:1, R = 0.3). IR (neat): ν 2959, 2928, 2887,
f
max
(
1) (a) Ortiz de Montellano, P. R. Cytochrome P-450, Structure,
Mechanism, and Biochemistry, 2nd ed.; Plenum Press: New York, 1995.
b) Gorrod, J. W. Biological Oxidation of Nitrogen; Elsevier/North
Holland Biomedical Press: New York, 1978.
2) (a) Murahashi, S.-I.; Zhang, D. Chem. Soc. Rev. 2008, 37, 1490.
b) Li, C.-J.; Li, Z. Pure Appl. Chem. 2006, 78, 935. (c) Murahashi, S.-I.
Angew. Chem., Int. Ed. 1995, 34, 2443.
(3) (a) Bernier, D.; Wefelscheid, U. K.; Woodward, S. Org. Prep.
Proced. Int. 2009, 41, 173. (b) Albini, A. Synthesis 1993, 263.
1
9
4
2
1
1
715, 1645, 1634, 1418, 1344, 1236, 1202, 1155, 1036, 1005, 970, 947,
−1
1
07, 741, 619, 594, 498, 436 cm . H NMR (400 MHz, CDCl ) δ =
3
(
.96−4.80 (m,1H), 4.44−4.33 (m, 1H), 2.76−2.62 (m, 1H), 2.58−
.47 (m, 1H), 2.46−2.27 (m, 2H), 2.22−1.93 (m, 5H), 1.83−1.71 (m,
(
13
H), 1.70−1.59 (m, 1H). C NMR (100 MHz, CDCl ) δ = 207.1,
67.0, 54.3, 50.7, 49.5, 48.7, 29.8, 27.9, 21.5. HRMS calcd for
3
(
+
C H NO (M + H), 168.1019; found, 168.1016.
9
14
2
2
0a
8-Benzoyl-8-azabicyclo[3.2.1]octan-3-one (3w).
114.6 mg,
50% yield. Isolated by flash column chromatography (ethyl acetate/
(
4) (a) Scheuermann, C. J. Chem.Asian J. 2010, 5, 436. (b) Li, C.-J.
1
petroleum ether = 1:2, R = 0.4). H NMR (400 MHz, CDCl ) δ =
7
2
f
3
Acc. Chem. Res. 2009, 42, 335. (c) Li, Z.; Li, C.-J. J. Am. Chem. Soc.
2005, 127, 3672.
.53−7.48 (m, 2H), 7.48−7.38 (m, 3H), 5.03 (s, 1H), 4.37 (s, 1H),
.99−2.83 (m, 1H), 2.60−2.23 (m,3H), 2.13 (s, 2H), 1.73 (d, J = 8.2
(5) (a) Ling, Z.; Yun, L.; Liu, L.; Wu, B.; Fu, X. Chem. Commun.
2013, DOI: 10.1039/C2CC37263K. (b) Do Pham, D. D.; Kelso, G.
F.; Yang, Y.; Hearn, M. T. W. Green Chem. 2012, 14, 1189.
(6) (a) Zhang, L.; Peng, C.; Zhao, D.; Wang, Y.; Fu, H.-J.; Shen, Q.;
Li, J.-X. Chem. Commun. 2012, 48, 5928. (b) Liu, W. P.; Liu, J. H.;
Ogawa, D.; Nishihara, Y.; Guo, X. W.; Li, Z. Org. Lett. 2011, 13, 6272.
13
Hz, 2H). C NMR (100 MHz, CDCl ) δ = 207.4, 168.8, 135.8, 130.5,
3
1
28.5, 127.0, 55.8, 51.3, 49.5, 48.7, 29.5, 27.9.
-Isobutyryl-8-azabicyclo[3.2.1]octan-3-one (3x). 101.5 mg,
2% yield. Isolated by flash column chromatography (ethyl acetate/
8
5
petroleum ether = 1:1, R = 0.5). Yellow oil. IR (neat): ν 2968, 2886,
f
max
−1
1
(
c) Li, H. J.; He, Z. H.; Guo, X. W.; Li, W. J.; Zhao, X. H.; Li, Z. Org.
Lett. 2009, 11, 4176.
1717, 1643, 1472, 1427, 1344, 1271, 1198, 1007, 984, 742 cm . H NMR
(
2
2
400 MHz, CDCl ) δ = 5.00−4.87 (m, 1H), 4.60−4.40 (m, 1H), 2.82−
3
(
7) (a) Li, Y.; Jia, F.; Li, Z. Chem.Eur. J. 2013, 19, 82. (b) Mai, W.-
.63 (m, 2H), 2.60−2.48 (m, 1H), 2.48−2.33 (m, 2H), 2.20−1.95 (m,
13
P.; Song, G.; Yuan, J.-W.; Yang, L.-R.; Sun, G.-C.; Xiao, Y.-M.; Mao, P.;
H), 1.87−1.59 (m, 2H), 1.16 (d, J = 6.8 Hz, 6H). C NMR (101 MHz,
Qu, L.-B. RSC Adv. 2013, 3, 3869.
(8) (a) Pattabiraman, V. R.; Bode, J. W. Nature 2011, 480, 471.
CDCl ) δ = 207.5, 173.8, 53.4, 50.8, 50.0, 49.0, 31.7, 30.0, 27.8, 20.1, 19.1.
3
+
HRMS calcd for C H NO (M + H), 196.1332; found, 196.1331.
11
18
2
(
b) Ekoue-Kovi, K.; Wolf, C. Chem.Eur. J. 2008, 14, 6302.
tert-Butyl 3-Oxo-8-azabicyclo[3.2.1]octane-8-carboxylate
4
3
(9) (a) Allen, C. L.; Williams, J. M. J. Chem. Soc. Rev. 2011, 40, 3405.
(3y). 153.1 mg, 68% yield. Isolated by flash column chromatography
1
(b) Allen, C. L.; Lapkin, A. A.; Williams, J. M. J. Tetrahedron Lett.
009, 50, 4262. (c) Valeur, E.; Bradley, M. Chem. Soc. Rev. 2009, 38,
606. (d) Comerford, J. W.; Clark, J. H.; Macquarrie, D. J.; Breeden, S.
W. Chem. Commun. 2009, 2562. (e) Montalbetti, C. A. G. N.; Falque,
V. Tetrahedron 2005, 61, 10827.
10) Grierson, D. The Polonovski Reaction. In Organic Reactions;
John Wiley & Sons, Inc.: New York, 2004.
11) Cooley, J. H.; Evain, E. J. Synthesis 1989, 1.
12) (a) Machara, A.; Cox, D. P.; Hudlicky, T. Adv. Synth. Catal.
(
ethyl acetate/petroleum ether = 1:1, R = 0.7). H NMR (400 MHz,
f
2
CDCl ) δ = 4.46 (s, 2H), 2.90−2.46 (m, 2H), 2.41−2.25 (m, 2H), 2.07
3
13
(s, 2H), 1.64 (d, J = 7.6 Hz, 2H), 1.47 (s,9H). C NMR (100 MHz,
CDCl ) δ = 208.4, 153.3, 80.2, 53.1, 52.9, 48.8, 48.5, 29.2, 28.6, 28.4.
3
tert-Butyl 3-Acetoxy-8-azabicyclo[3.2.1]octane-8-carboxy-
(
late (3z). 242.2 mg, 90% yield. Isolated by flash column chromatography
(ethyl acetate/petroleum ether = 1:1, R = 0.3). Colorless oil. IR (neat):
f
(
(
2
νmax 2974, 2882, 1738, 1694, 1394, 1366, 1238, 1165, 1101, 1078, 1034,
−1 1
870, 777 cm . H NMR (400 MHz, CDCl ) δ = 5.05 (t, J = 5.0 Hz, 1H),
3
012, 354, 2713. (b) Carroll, R. J.; Leisch, H.; Scocchera, E.; Hudlicky,
13
4
.16 (d, J = 32.7 Hz, 2H), 2.25−1.64 (m, 11H), 1.44 (s, 9H). C NMR
T.; Cox, D. P. Adv. Synth. Catal. 2008, 350, 2984. (c) Khai, B. T.;
Arcelli, A. J. Organomet. Chem. 1983, 252, c9. (d) Mariella, R. P.;
Brown, K. H. Can. J. Chem. 1971, 49, 3348.
(100 MHz, CDCl ) δ = 170.2, 153.3, 79.3, 67.9, 52.6, 51.8, 35.7, 35.0, 28.4,
3
+
28.2, 27.6, 21.5. HRMS calcd for C H NO (M + Na), 292.1519; found,
14 23 4
292.1518.
(
13) (a) Murata, S.; Suzuki, K.; Tamatani, A.; Miura, M.; Nomura, M.
tert-Butyl 3-Hydroxy-8-azabicyclo[3.2.1]octane-8-carboxy-
J. Chem. Soc., Perkin Trans. 1 1992, 1387. (b) Murata, S.; Tamatani, A.;
Suzuki, K.; Miura, M.; Nomura, M. Chem. Lett. 1990, 19, 757.
(c) Horner, L.; Winkelmann, E.; Knapp, K. H.; Ludwig, W. Chem. Ber.
1959, 92, 288.
(14) Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, I. Chem. Rev.
1999, 99, 1991.
2
0b
late (3y′).
50.0 mg, 22% yield. Isolated by flash column
1
chromatography (ethyl acetate/petroleum ether = 1:1, R = 0.4). H
f
NMR (400 MHz, CDCl ) δ = 4.28−4.16 (br, 1H), 4.16−4.03 (m, 2H),
3
13
2
.22−1.85 (m, 6H), 1.78−1.57 (m, 3H), 1.44 (s, 9H). C NMR (100
MHz, CDCl ) δ = 153.4, 79.0, 65.3, 53.0, 52.2, 38.6, 38.1, 28.5, 27.8, 28.3.
3
5
645
dx.doi.org/10.1021/jo400804p | J. Org. Chem. 2013, 78, 5638−5646